Method of removing hydrogen sulphide from hydrocarbon gases



Feb. 9, 1937. L, s. TwoMEY I METHOD OF REMOVING HYDROGEN SULPHIDE FROM HYDROCARBON GASES Filed May 9, 1954 Y LETWOMEY v /N VEN TOR 0 ORNEY i ical solution unduly expensive.

herein proposed removes all but a minor trace of UNI'I'ED STATES TPATENToFFlcE METHOD 0F lBEMOTING HYDBOGEN SUL- PBIDE FROM- HYDROCARBUN GASES 'Lee S. Twomey, Vista, Calif.

Application May 9, 1934, Serial No. 724,696

16 Claims.

The object of my invention is to provide means and a methodfor removing hydrogen sulphide from hydrocarbon g'ases such as natural gas, the

gas produced by cracking stills and other natural or artificial gases in which it may occur in large quantity or constitute an objectionable im-r purity.

In some natural gases, in particular, hydrogen sulphide often occurs in such large quantity as to render removal by water Washing or chemthis impurity, together with whatever carbon dioxide, ethane, and propane may occur in the raw material, and delivers a dry puried gas at pipe line pressure.

4 The attached drawing, to which reference is made in the following description, shows in highly diagrammatic form a complete apparatus suited to the performance of the method steps, andfhaving two alternative means for performing the nal step of separation.

Liquid anhydrous ammonia is stored in a receiver lIll from which it iiows through pipe II to and through an interchanger I2 in which it is supercooled to 196 K. by cold gases returned from a later stage in the treatment. From this interchanger a stream of liquid ammonia ows through pipe I3 to an expansion valve Ilby which it is admitted to the shell of a condenser of one atmosphere absolute, the ammonia evapcrates` in withdrawing heat from compressed f gaseous ethylene passing through theg tubes.` The vaporized ammonia, at atmospherictemperature and pressure, passes' through pipe I6 to Ya compressor I1 by which it is raised toa pressure of 7.5 atm. absolute. The compressed gas passes into a condenser I8 which is supplied with cold waterl as indicated by the arrows marked W". At 7.5 atm. absolute and atmospheric temperature the ammonia/ condenses, owilig through pipe I9 into receiver Il?, thus completing a closed ammonia cycle. The ammonia collects in this receiver at 7.5 atm." and 290 K.

Liquid ethylene is stored in a receiver 20 from which it ows through pipe 2| to and through a stream of liquid ethylene yflows through pipe 23v to an expansion valve' 24 by which it is admitted to one of the tube banks of a condenser 25.

' 'miese tubesv being maintained at a pressure of The treatment (Cl. (i2-175.5)

2.5 atm., the ethylene evaporates in withdrawing heat -from compressed gaseous methane owing through the shell. The vaporized ethylene at 2.5 atm. and 285 K. passes through pipe 26 to a compressor 21 in which its pressure is raised 5 to 18 atm. The compressed gas passes into a cooler 28 which is supplied with cold water, and

thence through pipe 29 to condenser I5 where it is cooled by evaporating ammonia, as described,

to a temperature of 240, at which it condenses 10 and iiows through pipe 30 into receiver 20, thus completing a closed ethylene cycle. The ethylene collects in this receiver at 18 atm. and 240 K. Liquid methane is stored in a receiver 30 from which it flows through pipe 3| to and through l5 the shell of an interchanger 32 in which it is supercooled to 151 K. by cold gases returned from a later stage in the treatment. From this v interchanger a stream of liquid methane flows through pipe 33 to an expansion valve 34 by which 20 Ait is admitted to the shell of an interchanger 35. This shell being maintained" at a pressure of-8.2 atm., the methane evaporates in withdrawing heat from a gas, later referred to, which is passing through the tubes. The vaporized methane at 8.2 atm. and 146 K. passes through pipe 36 to one of the tube'banks of interchanger 32 in which it is heated to 175 K. in assisting t`o` supercool the liquid methane, then through pipe 37 to one of the tube banks of interchanger 25 30 in which it is heated to 285 K. in condensing `compressed methane, and thence through pipe 38 toa compressor 39 in which its pressure is raised to 37.5 atm. The compressed gas passes into a cooler 40 which is supplied with cold water, 35 therce through pipe I2 to the shell oi.' condenser 25 where it is` cooled by evaporating ethylene and cold gaseous methane to 185 K., ,at which it condenses and ows through pipe I3 into receiver 30, thus completing a closed methane cycle. The 40 methane collects in this receiver at 37.5 atm. and 185 K.

The raw' gas to be treated enters the system through pipe and is raised by compressor 5I to a pressure of 10 atm. absolute. The compressed 45 cold water'and in which the heat of compression is removed. It then passes through pipe 53, at 10 atm. andI 290 K. into the shell of ajdehydrating interchanger 54, in which water present in the 50 gas is in part condensed and in part frozen. This interchanger is provided with bafiies and o with water drainsV 56, and to permit occasional de-icingshould be providedjin duplicate. with appropriate diversion pipes and valves. 55

The dehydrated gas passes from the cold end of the interchanger at 10 atm. through pipe 5l to the shell of an interchanger 58 in which' it is cooled to 195 K. under 10 atm. pressure. At this temperature the vapor pressure of hydrogen sulphide is 0.03 atm. and the partial pressure is 0.3% of the total pressure. Any hydrogen sulphide present in the gas in excesssof this percentage will be condensed in this interchanger and will ow, together with the residual gas, through pipe 59 into a liquid trap S0.

From this trap the liquefied hydrogen sulphide,

' if in sumcient quantity to be useful as a refrigerant, passes through pipe 6I toan expansion valve 62 by which it is admitted to one on the tube groups of interchanger 58. These tubes being maintained at atmospheric pressure, the liquid hydrogen sulphide evaporates in the upper part of the interchanger. The vaporized sul- `phide passes through pipe 63 to one of the tube groups of dhydrating ninterchanger d and is passed out of the system at substantially atmospheric temperature and pressure through pipe 54. Ii the condensate collecting in trap 60 be triiing in quantity; it `may be vented at intervals through f valve 68a. If the gas to be'operated on contains .so little hydrogen sulphide that no condensate may be expectedat this point, the trap may be omitted'from the assembly. u

From the top of trap 60 residual gas containing say 0.3% hydrogensulphide is directed through pipe 65 at 10 atm. and 195 K. into either separator 66a or 66h in which it is further cooled to 160^K. by admixture with a cycledcolder gas. At this temperature the vapor pressure of hydrogen sulphide is approximately 0.004 atm. and under an applied pressure of atm. the proportion of hydrogen sulphide remaining in the gas will be reduced to 0.04%, the difference between this residual quantity and the 0.3% entering the separator being reduced to the solid form, as snow crystals. As the method of producing this colder cycled gas and of separating the puried gas from solidiiied and liquefied products is subject to variation, it will be described at a later point.

As most natural gases, even when stripped of commercial gasoline by compression or absorption, contain highly material proportions of ethane and propane and traces of higher hydrocarbons, a liquid hydrocarbon condensate will be produced in separator 86 simultaneously with the congelation of hydrogen sulphide above described. 'I'he maximum quantities condensable in the' separator are indicated by the vapor pressures at 195 K. and at 160 K. At 195 K. the vapor presof propane is 0.17 atm. and at 160 K. is of. t e order of 0.03 atm. At an applied pressure or 10 atm. these partial pressures are equivalent to 1.7% and 0.3% respectively and the difference, or 1.4%, will condense in the separator provided the raw gas contained 1.7% or more of propane.

'If it contained a greater proportion than 1.7%, f

the excess would have been condensed in interchanger 58 and`withdrawn from trap 6.0 along with the liquefied hydrogen sulphide.

Similarly, the vapor pressure of ethane at 195 K. is 2-.0 atm. and at 160 K. is 0.2 atm., corresponding at 10 atm. applied pressure to 20.0% and 2.0% respectively, and the difference oi' 18.0% will condense in separator 66 if Rthe original gas cont ned 20% or over of ethane. In all cases the condensate in 66 will equal the originalpropane and ethane contents (up to 1.7% and 20.0%) less the amount remaining in the purifieds gas (0.3% and 2.0%) and BS it i D915 lmaovopae l common to encounter gases which contain nearly (a) to'separate the condensate and the solidk hydrogen sulphide from the puried gas;

(b) to separate the condensateA from the hydrogen sulphide crystals; I 1

(c) to remove the ysolid hydrogen sulphide from the system, and f (d) to remove the hydrocarbons from the system and recover their heat absorbing capacity by evaporation and interchange.

To eiect these steps we may use the apparatus shown in the lower right hand corner of the figure in the following manner. Separator' 66h,

which may be the well known cyclone separator or any suitable form of gas trap, 'separates the mist of condensatev and crystals from the mixed gases. The puriled gaspasses out of the separator through pipes 61h and 07 to one of the tube groups of interchanger 32, where it is heated to 175 in supercooling liquid methane, then through pipe 68 to interchanger 22 where it is heated to 184 in supercooling liquid ethylene, then through pipe SVS'to interchanger i2 where it is heated to 190 in supercooling liquid ammonia, then through pipe 10 to one of the tube groups of interchanger 58 and thence through pipe 1I to one ot' the tube group's of dehydrating interchanger 54, nally leaving the system through pipe 72 as puritled natural gas at substantially atmospheric temperature an`d at 10 atm. pressure.

In order to prevent freezing of the liquid ammonia in interchanger i2 by the relatively cold gas entering it through pipe-89 it is ,desirable to provide a bypass loop 73 controlled by a valve 14 vwhich is in turn controlled by a thermostat 75" or other temperature responsive device interposed in pipe i3. This device may be arranged to limit the temperature oi the liquid ammonia owing out of interchanger I2 to a minimum of 196 K.

The colder gas above referred lto as being intermixed with the gas stream from trap '60 is withdrawn, at 10 atm. and 160 K., from pipe 61 through a branch pipe I6 and introduced into the cold (lower) end of an interchanger l1. Froni the upper end of this interchanger the warm kgas passes through pipe 78 into a blower or other low head gas pump 'I9 by which it is forced through pipe 80 into a cooler 8| which is supplied with cold water. From this cooler the gas passes at atmospheric temperature through pipe 82 to the warm end of interchanger 7l. From this interchanger the gas passes at- 165 K.

blower 19 and to absorb any heat liberated in 2,070,098 'pipe 65, the discharge from Athe cyclone being 5.39

parts (assuming condensation of 0.04 part) of which 4.43 parts is cycled and 0.96 part passes out of the system. These gures do not include compensation for heat infiltration to the separator, and the actualproportion used will vary with the eectivenes of the Ainsulation provided.

The purpose of the interchange unit comprising interchanger 'l1 and cooler 8| is to permit kthe handling of warm instead of cold gas through the blowing mechanism. These two pieces of apparatus may be omitted if it is preferred to pump the gas cold.

'Ihe liquid condensate containing hydrogen sulphide crystals flows down the cone of separator 66h and passes, under a relatively low head produced by choking valve 81h, through either of pipes 88 or 89, which are provided with stop valves 90 and 9|, into one of a pair of ltering vessels 92 and 93. Each of these vesselsfis provided at a point near its upper end with a foraminous layer or ltering disc 94 which may be of vegetable bre, datomaceous earth, mineral or other wool or porous ceramic material of not too line porosity.

The liquid condensate passes upwardly through this filtering layer, which retains the crystals on its lower face, andflows through one of the stop valves 95 or 96 to a pipe 91h by which it is conducted to a junction with pipe 61 and is thus returned to the cold gas and introduced into interchanger 32 and to the later steps of interchange described for the puried gas.

The'condensate withdrawn from the lters is free from hydrogen sulphide and while the above `description contemplates its return to the puried gas in order to bring it back to its original constitution. the condensate may be withdrawn for useas such if of more value in the separated form.

Flow through one of the iilters is continued until Athe accumulation of a cake of crystals on the lower face of the filtering layer creates an undesirable back pressure. f the stream be now diverted to the other lter, or elsewhere, the cake tends strongly to drop from the disc and to subsideto the bottom of the vessel, the hydrogen sulphide crystals having approximately-twice the specific weight of the hydrocarbon condensate in which the cake is constantly immersed. If this step alone does not suiliciently clean the filter disc, one of the bottom valves 99 or |00 may be opened to aiord communication with pipe |0|, whichvents to the atmosphere at any point where `waste gases may be disposed of.

The reduction in pressure Within the lter vessel thus produced causes vapor to be generated above as well as below the filter disc, thus forcing liquiddown through its pores, thoroughly cleaning the lower side of the disc and placing it in condition for renewed use. in this manner a small amount of the condensate the ltersmay in` turn be cleared of hydrogen sulphide crystals without heating or the use of mechanical appliances. The liquid ltered being entirely free from solids other than the crystals, any more refractory stoppage of the disc may be clearedl away by entirely relieving the pressure and allowing the `filter to stand'l until it has warmed up to a temperature approximating K at which the hydrogen sulphide will be entirely gasied and dissipated.

'I'he use of filters and the loss of condensate may be avoided bythe use of the apparatus shown in the upper right hand corner of the gure.

By withdrawing() Referring to this portion of the iigure, the gas separated from the condensate in 66a passes through pipes 61a and 61 to interchanger 32 and thence out of the system through the path already described.

The condensate carrying hydrogen sulphide crystals in suspension flows downwardly from the cone through pipe |02 into the shell of an interchanger |03 in which it is heated to the melting point of solid hydrogen sulphide, 190 K., or a few degrees higher. At K. the vapor pressures of ethane and of hydrogen sulphide are materially below 10 atm. and no evaporation will be caused by this heating, but the hydrogen sulphide is liquefied. It is desirable to connect this interchanger with its warm end down, as shown, to prevent the melting of hydrogen sulphide in the upper end and its recongelation in the lower end.

The gas interchanged against the cold condensate to warm it to 190195 K. may be withdrawn from pipe 10 at the point indicated at |04, where the gas temperature is about 200 K. and passes through pipe |04 and valve 04a to the lower ends of the tubes of interchanger- |03. From the upper ends of the tubes the cooled gas returns to a junction with pipe 10 through pipe |05 and valve |05a at a point downstream from a choke valve |06.

The hydrocarbon condensate and the liquid hydrogen sulphide pass together through pipe |01 into a stratifying vessel |08. As the specic weightof liquid hydrogen sulphide is approximately twice that of liquid ethane, the liquids stratify rapidly. The liquid ethane-propane mixture is continuously drawn off through a valve |09 and pipe 91a to pipes 61a and 61 through which it passes to interchanger 32 and is ultimately returned to the purified gas leaving the Y system as previously described. The liquid hydrogen sulphide is withdrawn from the system 'through valve |l0 and pipe Il l which'leads to a point of use or disposal of hydrogen sulphide. Gauge cocks I |2 or other means for ascertaining the liquid level in the stratifying vessel |08 are desirable. f

The purified gas vented from the system at 12 is at substantially its initial pressure, and the energy residing in this compressed gas may be utilized to supply pat of the power required for y compression. Ordinarily this gas will be introduced into a pipe line operating at considerable pressure, and while in the example above given a pressure of 10 atm. was taken byway of illustration, it ispossible to operate the system at such pressure as to pass the gas directly' into the line without `'either raising or lowering the pressure. thus reducing the power` consumption to that required for refrigeration plus the small amount required to cycle the cooling gas under a balanced pressure and to move the gas through the system.

The temperatures and pressures set forth in the above description are intendedV to be illustrative only, though they set forth a desirable combination of conditions for this specic purpose. It will be understood that they are subject to variation over a fairly wide range, both as to pressure carried on the gas supplied and the temperatures to which it is cooled in various stages. The general method set VJforth is also applicable to other gases containing bodies subject to congelation, such-for example as carbon dioxide, sulphur dioxide, and various unsaturated hydrocarbons, and is by no means limited to the treatment of the natural gas described.

I claim as my invention:

from natural gas which comprises: compressing a stream of said gas; removing the heat of compression from said stream; cooling said stream to a temperature below the freezing point of water,

whereby said stream is"substantially dehydrated; further cooling said stream to approximately 195 K.; separating from said stream any hydrogen sulphide liqueedinh said further cooling step; introducing said stream into a chamber and intermixing with said stream a cycled stream of puried gas previously cooled to approximately 151 K., the volumetric proportions of said streamsk being such that the temperature of the mixture in said chamber is maintained at approximately 160` K., whereby substantially all the-hydrQgen sulphide remaining in rs't said streamds frozen and hydrocarbon constituents of said gas are condnsed; withdrawing from said chamber a stream of said condensate entraining frozen particles of hydrogen sulphide; separating said particles from from natural` gas which comprises: cooling 'a stream of said gas to a temperature slightly above the freezing point of hydrogen sulphide; separating from said stream any substances liquefied by said cooling; intermixing with said stream a previously cooled cycled stream of gas, the temperature of Ysaid cycled stream andthe relative volumes of said streams being such that the temperature of the intermixed stream is below the freezing .point of hydrogen sulphide; submitting said stream to a centrifugal effect whereby tfrozen particles of hydrogen sulphide and any hydrocarbons condensing at last said temperature are separated from the gaseous portion of said stream;

ywithdrawing said frozen particles with said condensate and separating said particles from said condensate; withdrawing the gaseous stream from said centrifugal effect; returning said condensate to said withdrawn gaseous stream; discharging from the system a portion of last said stream substantially equal in volume to the initial stream less the substances withdrawn therefrom, and cooling the remainder of 'said stream to supply said cycled stream.

3. The method of separating hydrogen sulphide from natural gas which comprises: cooling a stream of said gas to a. temperature slightly above the freezing point of hydrogen sulphide;

` separating from said stream any substances liquefied by said cooling; intermixing with said stream a previously cooled cycled streamiof gas,

, the temperature of said cycled steam andthe relative volumes o f said streams being such that the temperature of the intermixed stream is below the freezing point of hydrogen sulphide; separating from the gaseous portion of said stream frozen particles of hydrogen sulphide and any hydrocarbons condensing at last said temperature and separating said frozen particles from said condensate; withdrawing the gaseous ,stream from said separating effect; returning said condensate to said withdrawn gaseous stream; disl. The method of separating hydrogen sulphide stream substantially equal in volume to the initial stream less than the substances withdrawn therefrom, and cooling the remainder of said stream to supply said cycled stream.

4. The method of separating hydrogen sulphide from natural gas which comprises: cooling a stream of said gas to a temperature slightly above the freezing point of hydrogen sulphide;` separating from said stream any substances liquefied by said cooling; intermixing with said stream a previously cooled cycled stream of gas, the temperature of said cycled stream and the relative volumes of said streams being such that the tem- "perature of the intermixed stream is below the freezing point of hydrogen sulphide; submitting said stream to a centrifugal effect whereby frozen particles of hydrogen sulphide and any hydrocarbonscondensing at last said temperature are separated from the gaseous portion .of said stream; withdrawing said frozen particles with said condensate; withdrawing the gaseous stream from said centrifugal effect; vdischarging from the system a portion of last said stream substantially equal in volume to the initial stream less the substances withdrawn therefrom, and cooling the remainder of said stream to supply said cycled stream.

5. The method of separating hydrogen sulphide from natural gas which comprises: cooling a stream of said gas to a temperature slightly above the freezing point of hydrogen sulphide; separating from said stream any substances liquefied by said cooling; intermixin'g with said stream a previously cooled cycled stream `,of gas, the temperature of said cycled stream and the relative volumes of said streams being such that the temperature of the intermixed stream is below the freezing `point of hydrogen sulphide; separating from the gaseous portion of said stream frozen particles of hydrogen sulphide and anyv hydrocarbons condensing at last said temperature; withdrawing the gaseous stream from said separating effect; discharging from the system a portion of last said stream substantially equal in volume to the initial stream less the substances withdrawn therefrom, and cooling the remainder of said stream to supply said cycled stream.

6. The method of separating hydrogen sulphide from' natural gas which comprises: stream of said gas to a temperature slightly above the freezing point of hydrogen sulphide: intermixing with said stream a previously cooled cycled less thesubstances removed therefrom, and cooling the remainder of said stream to supply said cycled stream.

cooling a 7. Themethod of separating hydrogen sulphide from natural gas which comprises: cooling a stream of said gas to a temperature slightly 'above the freezing point of hydrogen sulphide; intermixing with said stream a previously cooled cycled drogen sulphide; separating from the gaseous portion of said stream frozen particles of hydrogen sulphide; withdrawing the gaseous stream from said separating effect; discharging from the system a portion of last said stream substantially equal in volume to the initial stream less the substances removed therefrom, and cooling the remainder of said stream to supply said cycled stream.

8. The method of separating hydrogen sul phide from admixture with natural gas which comprises: cooling a stream of said gas to a temperature above the freezing point of hydrogen sulphide; cooling said stream by intermixture with a colder gas stream to a temperature at which hydrogen sulphide is frozen and a hydrocarbon condensate is formed; separating said condensate together with entrained frozen particles of hydrogen sulphide from said gaseous intermixture, and separating said frozen particles from said condensate.

9. A method substantially as and for the purpose set forth in claim8, including the step of returning said condensate to said gaseous intermixture after separation of said frozen particles.

l0. A method substantially as and for the purpose set forth in claim 8, in which the condensate and entrained frozen particles are raised to a temperature above the melting point of said particles under such pressure conditions as to maintain said condensate substantially liquid, and the melted particles are collected in a layer below said condensate and withdrawn from said layer in liquid form.

l1. A method substantially as and for the purpose set forth in claim 8, in which said frozen particles are separated from said condensate by ltration.

12. A method substantially as and for the purpose set forth in claim 8, in which said frozen particles are separated from said condensate by sedimentation.

13. In a gas fractionating operation including the cooling of a gas stream by intermixture with a cycled stream of gas previously brought to a lower temperature, the steps comprising: dividing said cooled intermixed stream to produce a discharge streamand a cycled stream; withdrawing said discharge stream; heating said cycled stream to substantially atmospheric temperature by a step of heat interchange; mechanically impelling said cycled stream through its cycle; removing from said cycled stream any heat liberated in said impelling step and passing said impelled stream through said heat interchange step whereby the stream passing to the impelling step is heated and the stream passing from the impelling step is cooled, and further cooling said stream to the temperature required for the step of intermixture.'

14. Steps substantially as and for the purpose set forth in claim 13, in which the cooling step is produced by heat interchange with an expanded and' evaporating liquid refrigerant` 15. Steps substantially as and for the purpose set forth in claim 13, in which the cooling step is produced by heat interchange with expanded and evaporating liquid methane and the gas stream consists of natural gas.

16. In'a refrigeration system involving the production of a series of refrigerant liquids by condensation at successively lower temperatures, the step of subcooling streams of said liquids by passing a stream of cold gas in heat interchange relation with a succession of said liquid streams in the order of rising condensing temperature.

LEE S. TWOMEY. 

